Non-silver photosensitive printout compositions



United States Patent (Mike 3,342,604 NON-SILVER PHOTOSENSITIVE PRINTOUT COMPOSITIONS Robert H. Sprague, Chagrin Falls, John A. Stewart, Parma, and James M. Lewis, Cleveland, Ohio, assignors to Horizons Incorporated, a corporation of New Jersey N Drawing. Filed Sept. 28, 1964, Ser. No. 399,892 12 Claims. (Cl. 96-90) ABSTRACT OF THE DISCLQSURE Non-silver photosensitive compositions which printout an image directly as a result of exposure to visible light and containing the following, in admixture: (1) a suitable color forming leuco-compound; (2) a styryl dye base or a cyanine dye base; (3) an organic halogen compound; and (4) a non-toxic colorless organic sulfur containing compound.

The leuco compounds suitable for the photosensitive compositions of this invention are described in copending United States patent applications Ser. Nos. 270,551 filed Apr. 4, 1963 and issued Nov. 15, 1966, as United States Patent 3,285,744 and'395,903 filed Sept. 11, 1964, by R. H. Sprague et al., the disclosures of which are incorporated herein by reference.

These compounds are represented by the following general formulas R is H, lower alkyl or aryl; and R is H, alkyl or aryl including (2) The dye bases The dye bases which provided enhanced speed and density and which cause a shift in the hue of the printout image towards the blue in some instances are the 3,342,604 Patented Sept. 19, 1967 ularly those exemplified in the examples which follow.

These dye bases are represented by the following general formulas:

wherein R and R represent monovalent radicals selected from the group consisting of lower alkyl tie, methyl, ethyl, n-propyl) and benzyl, and may be the same as one another or different from one another; R" represents a monovalent radical selected from the group consisting of H and CN; d and it each represents a positive integer which is either 1 or 2; m is a positive integer not greater than 4; and the sum of n1 and m-1 is not greater than 4; and Q represents the nonmetallic atoms necessary to complete a heterocyclic nucleus (i.e., the atoms of C, O, S, Se, and N) necessary to complete heterocyclic compounds such as those in United States Patent 3,102,810.

I H=CH)a 1C= CCH H-;=C-CXJ=(CIE[ CH)Q I=N wherein d and e each represents a positive integer of from 1 to 2; n represents a positive integer of from 1 to 4; R

represents an organic radical selected from the group conthe same carbon atom is attached to two non-carbon sisting of alkyl, aralkyl and aryl groups; R represents hydrogen or a cyano group; R represents H or alkyl; and Q and Z each represents the nonmetallic atoms necessary to complete a heterocyclic organic nucleus containing from 5 to 6 atoms in the ring.

(3) The activators The organic halogen compounds and non-toxic sulfur compounds should be present in the photosensitive compositions of this invention in amounts between about 5 and 50 parts by weight for each part by weight of leucoxanthene or leuc-o-anthracene compound.

Suitable organic sulfur compounds are those selected from the group consisting of: R is a heterocyclic nucleus of the type commonly used (1) Mercapto compounds of the type RS-H wherein R is a heterocyclic nucleus of the type commonly used in cyanine dye chemistry (as in the above noted patent);

(2) Disulfides of the type RSS R wherein R has the same meaning as in 1 above;

(3) Disulfides of the general formula S I! II O-N-R wherein R" is selected from the lower alkyl and aryl;

(4) Cyclic sulfur compounds wherein the sulfur is attached to a carbon atom in a heterocyclic ring wherein group consisting of H,

atoms e.g. as in rhodanine or tetrazole;

(5) Thiourea and substituted thioureas; (6) Acyclic thioacetanilides; and (7)' Rhodanines. The non-toxic colorless sulfur containing organic com- 3 4 pound is preferably present in the photosensitive composi- Other binders which have been found to be useful in tions of this invention in amounts between 0.1 and 10 the compositions of the present invention include: parts by weight for each part by weight of leuco-xanthene Ethyl cellulose in ethanol, or leuco-anthracene compound. Nitrocellulose in methanol, The invention will be better understood from a con- 5 Polystyrene in benzene, sideration of the data presented in the following table, Polyvinylidene chloride copolymer in methyl ethyl kein which the results obtained by exposing mixtures contone, sisting of the leuco compound and activators are con- Polyvinyl ill y trasted with the results obtained by exposing similar mix- It Will be evident that other Compatible and chemically tures containing in addition a small amount of a suitable inert binders m y he used in Place of those lleled above dye b without departmg from the scope of the 1nvent1on.

In each instance a binder solution of cellulose acetate Having newheserlhed the invehlloh it is not intended butyrate in acetone and benzene was formulated and to that It be hmlted eXeePt as reqhlred y the pp this the carbon tetrabromide and Z-mercaptobenzothiazole elahhswere added. Then, when it was present, the dye base was We elalm: 1

added. The formulations described in the examples which A hoh'shver composition which 'f f visible follow comprised the following; image directly as a result of exposure to v1s1ble llght said composition consisting essentially of Acetone 2 a leuco compound represented by the general formula Benzene cc 2 R R Cellulose acetate butyrate "mg-.. 100 z 1 Leuco compound mg 100 CBr mg 700 R, R1 Z-mercaptobenzothiazole mg Dye base (when present) mg 100 25 wherein each R is selected from the group consist- The resulting mixture was coated as a 0.003 inch wet lhg of H, lower alkyl, and aryl, and the Several 1 coating hi k on sheets f type 302 Mylar 1 neednot all be the same; Z is selected from the group ethyleneterephthalate). After the coating was permitted eohslshhg of and to dry, it was then exposed for 1 minute to illumination R from one photofiood lamp at a distance of 12 inches lamp to film, through a step tablet with red, green and blue filters. The resulting densities and number of steps visible R is reported below; wherein R represents H or alkyl; and Q 1s selected from the group consisting of Example Leuco Compound Dye base \N/ \C/ and 1 3,6-bis (dimethylamino)-9- None. H H

g g g g y -p y wherem R is H, alkyl or aryl; 2 Asinlabo've 4 [3 3 ethy 1 2(-3H)bemo 40 an activator consisting of (a) at least one organic g g g y p y halogen compound represented by the general for- 3 4 (3 hy1 2(3H) benZ0thia mula AC-X wherein A represents a monovalent gg d we y n radical selected from the group consisting of H, Cl, 4 2,7-bis (dlmethylamino)-9, None, Br, unsubstituted alkyl, substituted alkyl (particuy larly haloalkyl), aralkyl, unsubstituted aryl, substi- 5 l i tuted aryl and aroyl and each X is a halogen atom sm a ove Asin2above. 4 6 gh gh f;g gliggggg selected from the group consisting of Cl and Br and 9.1gd1h dm-9,9-d1meth 1 (b) at least one organic sulfur compound selected all C AS in i gfif As in 2 above. from the group consisting of -ifiggaruggivfdfee N Do. (1) mercapto compounds represented by the fori 4 ("glfi'imethylammostyryn mula RSH where1n R is a heterocychc nuquinoline. cleus represented by the formula commonly used in cyanine dye chemistry;

Clear Red Green Blue Base Example plus Image Hue Fog N0. Gross Net No. Gross Net No Gross Net N0. Gross Net Steps Steps Steps Steps 0. 34 21 3+ 2. 66 11 2. 94 2. 60 1s 1. 77 1. 43 16 2.81 2. 47 Magenta. 0.12 21 3+ 2. 88 21 2. 93 2. s1 21 3+ 2. 88 21 2. 86 2. 74 B Lie. 0. 21 21 3+ 2. 84 13 3+ 2. s4 21 2. 6 2. 44 21 3+ 2. 84 Reddish Orange. 0. 06 21 3+ 2. 94 15 1. 0s 1. 02 11 1. 06 1. 00 15 1. 46 1. 40 Blue. 0. 16 21 3+ 2. s4 21 2. 70 2. 54 20 2. 35 2. 19 16 2. 54 2.38 o. 0.06 18 1. 55 1. 49 12 1. 25 1.19 9 1. 27 1. 21 12 0.66 0. Do. 0.08 21 1.69 1.61 21 1. 56 1. 48 21 1. 46 1. 38 1e 1. 23 1.17 Do. 0. 07 21 1. 52 1. 45 21 1. 55 1.48 19 1. 44 1. 39 16 1. 31 1. 24 Do. 0. 05 13 1. 00 0. 95 6 0. s5 0. 79 5 0. 24 0. 19 s 0. 25 0. 20 Do. 0. 05 17 1. 76 1. 71 9 1. 86 1. 81 11 1. 01 0. 96 10 0. 71 0. 66 Do.

It will be seen that with the dye base present the density 70 (2) disulfides of the type R-SSR wherein was enhanced and the image was shifted toward the blue, R has the same meaning as in 1 above; a more pleasing color for printed copy. disulfides 0f the g r r a Instead of including a binder in the sensitive compo- R S R sition, the composition without binder can be applied to E I -S-SCNR" an absorbent porous substrate such as paper.

wherein R" is selected from the group consisting of H, lower alkyl and aryl;

(4) sulfides wherein the sulfide is attached to a carbon atom in a heterocyclic ring wherein the same carbon atom is attached to two non-carbon atoms;

(5) thiourea and substituted thioureas;

(6) acyclic thioacetanilides; and

(7) rhodanines;

and a dye base selected from the group consisting of styryl dye bases and cyanine dye bases.

2. The composition of claim 1 wherein the leuco compound is a leuco-xanthene.

3. The composition of claim 1 wherein the organic halogen compound is CBr 4. The composition of claim 1 wherein the organic sulfur compound is a heterocyclic compound in which a mercapto group is attached to the number 2 carbon in the heterocyclic nucleus.

5. The composition of claim 3 wherein compound is Z-mercaptobenzothiazole.

6. The composition of claim 1 wherein the styryl dye base is 4-p-dimethylamino styryl quinoline.

7. The composition of claim 1 wherein the cyanine dye base is 4-[3-(3-ethyl-2(3H) benzothiazolylidene)-propenyl] quinoline.

the mercapto 8. A dry film consisting of the composition of claim 1 dispersed in a thin layer on an inert support.

9. The film of claim 8 wherein the support is a film forming plastic.

10. The film of claim 8 wherein the thin layer contains a cellulose compound selected from the group consisting of cellulose and cellulose derivatives as a binder for the constituents in the mixture.

11. The film of claim 8 wherein the support is transparent.

12. The process of producing a direct print-out image from originally colorless compounds which comprises preparing the composition of claim 1 in the form of a thin layer, exposing said layer to a pattern of visible light whereby a visible image prints out directly as a result of said exposure.

NORMAN G. TORCHIN, Primary Examiner. C. E. DAVIS, Assistant Examiner. 

1. A NON-SILVER COMPOSITION WHICH PRINTS OUT A VISIBLE IMAGE DIRECTLY AS A RESULT OF EXPOSURE TO VISIBLE LIGHT SAID COMPOSITION CONSISTING ESSENTIALLY OF A LEUCO COMPOUND REPRESENTED BY THE GENERAL FORMULA 